Lubricant and additives therefor



United States Patent 3,259,577 LUBRICANT AND ADDITIVES THEREFOR PierreM. Coant, Woodbury, and Francis G. A. de Monterey, Woodbury Heights,N.J., assignors to Socony Mobil Oil Company, inc, a corporation of NewYork No Drawing. Filed Feb. 19, 1963, Ser. No. 259,736 Claims. (Cl.25233.3)

This invention has to do with lubricating compositions and with acombination of additives therefor.

It is known that a variety of materials can be dispersed in lubricatingoils to impart desirable improvements thereto. Calcium acetate is onesuch material. It is particularly advantageous in regard toload-carrying ability and antiwear properties. Because of itsacid-neutralizing ability, calcium acetate is a particularly desirableadditive for lubricating oils used in engines operated on highsulfur-content fuels, such as marine diesel engines.

Simple dispersions of calcium acetate in lubricating oil, however, areunstable, the calcium acetate separating out during transportation and/or storage of the oil composition. In order to overcome this problem andobtain insofar as possible the advantages provided by calcium acetate,particularly in fluid lubricants such as marine diesel oils, it has beenthe practice to employ emulsion type oils, i.e., those formed byemulsifying a water solution of calcium acetate with lubricating oil.These emulsion oils, however, have not been entirely satisfactory. Thus,due to their water contents, they tend to increase the corrosion problemand they are unstable under the varying conditions encountered instorage and use. For example, the high temperatures encountered duringstorage in the engine rooms of ships tend to break the emulsion. On theother hand, under the low temperature conditions often encountered incold climates, the aqueous phase can become frozen so that the emulsionis destroyed.

Present day, large marine diesel engines operate under rigorousconditions and impose severe demands upon lubricating oils used therein.Specifically, clogging of cylinder exhaust ports is a serious problem.As more of the ports become clogged, lubrication efficiency is reducedand, ultimately, failure of one or more engine partssuch as pistonringsresults. Not only is the extent of port clogging of importance, butso, too, is the nature of the deposits formed by decomposition ordegradation of the oil used to lubricate the cylinders and of one ormore of the additives generally present in the oil. Tacky, varnish-likedeposits are diflicult to remove from the engine and cause wear onmoving engine parts, such as pistons; whereas, soft grease-like depositsare not disadvantageous.

It will be appreciated, therefore, that stable dispersions of calciumacetate in lubricating oil would be of .considerable value, since such asingle-phase oil avoids the aforementioned disadvantages of an emulsiontype oil. Still of further value, however, would be such stabledispersions so fortified that port deposits and wear on engine parts, asdescribed above, are minimized. It is with such stable dispersions ofcalcium acetate and lubricating compositions containing the same thatthis invention is concerned.

It is an object of the present invention, therefore, to providelubricating compositions capable of effectively lubricating machineryoperated under rigorous conditions. A particular object of the inventionis to provide lubricating compositions effective in large marine dieselengines without formation of substantial cylinder port deposits and withminimal wear of engine parts. Another object is to provide suchcompositions characterized also by load carrying characteristics(ability to withstand extreme pressures) and capacity to neutralizesulfur-containing acids formed during the combustion of high-sulfurfuels in Ice diesel engines. Still another object of the invention is toprovide mineral oil concentrates containing particularly effectivecombinations of additives for use in lubricant compositions. A furtherobject of the invention is to provide new compositions of mattercomprising combinations of additives which can be incorporated inlubricating oils to enhance the lubrication value thereof. Additionalobject will be apparent from the following description.

In a study to develop a single phase lubricating oil which could be usedin large marine diesel engines with only low port deposit formation,while also aifording excellent load-carrying characteristics anddesirable neutr-alization of sulfur-containing acids formed duringcombustion of high-sulfur fuels, it has been found, surprisingly, thatextremely low Wear of engine parts is realized in addition to achievingthe aims of the study, when particular combinations of additives,including calcium acetate, are used in lubricating oils. The new oilcompositions so discovered, and forming the basis of this invention,comprise:

(a) A major proportion of a mineral lubricating oil,

(b) From about 1 to about 20 percent by weight of the composition ofcalcium acetate,

(0) From about 0.01 to about 3 percent by weight of the composition of aN-acyl-substituted sarcosine compound of the formula wherein Rrepresents an aliphatic hydrocarbon radical of from 8 to 24 carbonatoms,

(d) From about 0.1 to about 10 percent by weight of the composition ofan oil-soluble metal sulfonate, and

(e) From about 0.1 to about 5 percent by weight of the composition of anoil-soluble, phosphorusand sulfur-containing reaction product obtainedby reaction at a temperature between about C. and about C. ofsubstantially one mole of a phosphorus sulfide and four moles of amaterial selected from the group consisting of a dicyclic terpene and anessential oil predominantly comprised of a dicyclic terpene.

Contemplated herein also are oil concentrates containing the additivesidentified as (b) through (c), immediately above, and new compositionsof matter comprising combinations of said additives (b) through (c).

Proportions of the additives are of importance in order to obtain theunusual and unexpected combination of desirable results therewith. Inthis connection, calcium acetate (b) should be present in the oilcompositions in concentrations of at least about 1 percent by weight,otherwise the compositions have inadequate load carrying capacity(extreme pressure characteristics). Correspondingly, the maximumconcentration of calcium acetate in the oil compositions should notexceed about 20 percent by weight thereof, to avoid excessively highviscosity of the compositions and formation of grease or gel structures.Preferred concentrations of acetate are from about 2 to about 8 percentby weight. With respect to the sarcosine compound (c), concentration canvary between about 0.01 to about 3 percent by weight, with a preferredapproximate range of 0.1 to 1. In general, larger amounts of thesarcosine compound are used with larger amounts of calcium acetate, andsmaller with smaller amounts of the latter. The metal sulfonate (d)concentration ranges from about 0.1 to about 10 percent by weight, andpreferably 1 to 5. Here again the concentration of the sulfonate isrelated to the concentration of the acetate, e.g. larger amounts ofsulfonate accompanying larger amounts of acetate. The use ofinsufiicient concentrations, or of excess, sulfonate is to be avoided,lest inferior compositions be formed. That is, dispersions may beunstable and show sedimentation, or viscosity control may be vitiated.And the concentration of the reaction product (e) is controlled betweenabout 0.1 to about percent by weight of the oil compositions; thepreferred range is 1 to 3. Here, too, insufiicient reaction productleads to higher wear rate and too large a concentration causes poorwater resistance properties. I

The total quantity of additives (b) through (e) in the oil compositionsof this invention, therefore, will range from about 1 to about 35percent by weight. In marine diesel engine oils, particularly thoseoperated on high sulfur content (l5 percent sulfur) fuels, the totalquantity is generally at the higher end of the range, namely, topercent. While emphasis has been placed there on oil composition formarine diesel engines, it is to be understood that the new oilcompositions can be used to lubricate other equipment. For example, oilsdesigned for lubrication of small 2-stroke diesel engines operating onlow-sulfur fuel (up to 1%) will contain a total of l to 6 percent ofadditives (b) through (c).

As pointed out above, :oil concentrates are also contemplated by thisinvention. Thus, much less oil can be used with the combination ofadditives than in oil compositions in condition for use in an engine, toform a concentrate and the concentrate can thereafter be diluted withadditional oil to form the desired oil compositions. Concentrates areparticularly desirable since they can be prepared in one refinery orrelated plant and can then be shipped to other localities where suchfacilities are lacking but where blending equipment is available.Considerable savings in transportation and equipment costs can berealized. A further extension of this feature is that of preparingmixtures of the additives free of oil and transporting the mixtures tolocations Where they can be incorporated in oil for formation of thedesired oil compositions. In the mixtures, the parts by weight of theseveral additives are as follows:

It is to be understood that the amount of each additive set forththroughout this application is expressed on an oil-free basis, unlessotherwise specified.

Lubricating oils (a) contemplated herein can vary widely in origin andcharacteristics. Naphthenic base, parafiin base, Coastal base, and mixedbase mineral oils are representative. Other hydrocarbon lubricantsinclude lubricating oils derived from coal products and alkylenepolymers such as polymers of propylene, butylene, etc., and mixturesthereof. Synthetic oils other than composed of hydrogen and carboninclude: alkylene oxide polymers, dicarboxylic acid esters, liquidesters of phosphorus, polypropylene glycol, di-(2-ethyl hexyl) sebacate,di-(Z-ethyl hexyl) adipate, trimethylolpropane tricaprylate and relatedesters of pentaerythritol, neopentyl glycol, and the like. In general,the hydrocarbon oils and synthetic vehicles which can be used herein arecharacterized by a viscosity (S.U.S.) of greater than seconds at 38 C.(100 F.), preferably from 100 to 2000 seconds at 38 C. Outstanding foruse in the oil compositions particularly adapted for large marine dieselengines are solvent-refined Coastal oils, and mixtures thereof, havingviscosities of 150-700 seconds at 38 C.

The quantities of lubricating oil, or oils (a), in the oil compositionsare of the order of about 65 to about 99 percent by weight, andpreferably to 85. It follows that the oil concentrates of this inventionwill contain lesser quantities of the oil, or oils (a), than the oilcomwherein R represents an aliphatic hydrocarbon radical having from 8to 24 carbon atoms and which can be either saturated or unsaturated.Typical examples are the following sarcosines:

N-pelargonyl N-oleyl N-undecyloyl N-linoleoyl N-lauroyl N-arachidoylN-myristoyl N-behenoyl N-palmitoyl N-hyenoyl N-stearoyl SeveralN-acyl-substituted sarcosines are available commercially under the tradename Sarkosyl, for example, Sarkosyl-L (lauroyl sarcosine), Sarkosyl-O(oleyl sarcosine) and Sarkosyl-S (stearoyl sarcosine).

Preferred for the compositions of this invention is oleyl sarcosine.

All oil-soluble metal sulfonates, (d) above, are contemplated by thisinvention. This sulfonic acids used in forming the sulfonates includeoil soluble petroleum sulfonic acids and synthetic alkaryl sulfonicacids, particularly those having higher molecular weights, i.e., fromabout 300 to about 800. These sulfonic acids may be produced bysulfonation of petroleum stocks or synthetic alkyl aromatic compounds,such as alkyl-substituted benzenes or naphthalenes wherein the alkylgroups attached to the aromatic ring contain from at least about 8 toabout 24, or more, carbon atoms. Specific synthetic sulfonic acids are,for example, octyl benzene sulfonic acid, dodecyl benzene sulfonic acid,dioctyl benzene sulfonic acid, octadecyl benzene sulfonic acid, waxbenzene sulfonic acid and wax naphthalene sulfonic acid.

All metals are contemplated herein as constituents of the sulfonates.Most suitable are calcium, barium and magnesium. When the metalconstituent is polyvalent, basic as well as neutral metal sulfonates canbe formed; all serve the purposes of this invention. Preferred is aslightly basic calcium petroleum sulfonate.

The oil-soluble, phosphorusand sulfur-containing reaction products (e)above, contemplated herein are those obtained by reacting a dicyclicterpene and a phosphorus sulfide at a temperature above about C.Although any one of the several phosphorus sulfides such as a s 2), P4862 3), P483: 2 5 4 10) P 8 etc., may be used in the preparation of thesaid reaction products, particularly preferred are those reactionproducts obtained from P 8 Dicyclic terpenes are defined herein as thoseterpenes which are characterized by the presence of one double bond inthe molecule and which are comprised of two ring systems. Typical ofsuch terpenes are pinene, carnphene and fenchene. Contemplated as comingwithin this particular designation are those materials which arepredominantly comprised of one or more dicyclic terpenes; representativeof such materials are the essential or volatile oils which arepredominantly comprised of such a terpene, or terpenes, and are typifiedby turpentine oil, the predominant constituent of which is pinene.Preferred of the dicyclic terpene reactants are pinene and turpentineoil. Accordingly, the preferred reaction products are those obtainedfrom P S and pinene and from P 8 and turpentine oil.

Further details of the reaction products (e) are provided in US. PatentNo. 2,416,281 of Henry G. Berger et a1. and reference is made herein tothe patent disclosure.

In preparing the oil compositions of the invention, a stabilizeddispersion of the calcium acetate, employing the sarcosine compound asthe stabilizing agent, is prepared separately. This is accomplished byintimately mixing the several components, i.e., oil, calcium acetate andsarcosine, preferably in a Manton-Gaulin Homogenizer operated at apressure of from about 1000 to about 5000 psi. The other components,including additional oil, if desired, are then mixed with the stabilizeddispersion at temperatures ranging from to 100 C., and preferably about90100 C.

Examples illustrating and in no sense limiting the invention are givenbelow. All parts are by weight in the examples unless otherwisespecified.

ILLUSTRATIVE EXAMPLES Example 1 Mineral oil, 57 parts, and calciumacetate, 40 parts, and oleoyl sarcosine, 3 parts, were charged to agrease kettle equipped with a paddle type mixer, in the order specified.The resulting mixture was heated with stirring to 138 C., held at thistemperature for 20 minutes and cooled with continued agitation to roomtemperature (about C.). It was then homogenized when passed once througha Manton-Gaulin Homogenizer operated at 3000 pounds per square inch(p.s.i.). The resulting high- 1y stable dispersion of calcium acetate isidentified hereinafter as Product 1.

The mineral oil used was a solvent-refined naphthenic (Coastal) oilhaving a viscosity (S.U.S.) of 500 seconds at 38 C. Calcium acetatecontained 6 percent of water, i.e., approximately 2/3 mole Water ofhydration.

Example 2 A Mid-Continent distillate of 95 seconds Saybolt viscosity at38 C. was treated with oleum, the resulting sludge was settled andremoved, and the oil layer which formed was neutralized with causticsoda solution. The sodium sulfonates thus formed were recovered byadding ethyl alcohol, separating the resulting alcohol layer, and thenevaporating off the alcohol. This left a mixture of oil and sodiumsulfonates. This mixture was then reacted with a water solution ofbarium chloride. After separation of the oil layer and drying, theresulting oil solution of barium petroleum sulfonate (Product 2)contained 6.9% barium and 2.5% sulfur.

Example 3 A mineral oil solution of a slightly basic calcium petroleumsulfonate (about active ingredient), identified hereinafter as Product3, was used. This material has the following properties:

Gravity, API 15.6 Flash point, C. 243 S.U.S. 99 0, secs. 1100 Calcium,weight percent 1.7 Sulfur, weight percent 2.7 Base number 8.0

Example 4 Eight hundred (800) parts by weight of pinene and an equalweight of motor oil (Saybolt Universal Viscosity of seconds at 99 C.)were heated at 105 C. with stirring. Three hundred and twenty-six (326)parts of P S (a ratio of 4 moles of p-inene to 1 mole of P 8 were addedslowly, the temperature rising to 115 C. because of the exothermicreaction. The mixture was then heated and the resultant mixture wasfiltered. The filtrate, consisting of 1842 parts by weight, was thenvacuum topped at 5 mm. pressure to a pot temperature of 150 C. Theresidue consisting of 1963 parts by weight was a 6 clear, viscousoilProduct 4--containing 12.5% sulfur and 5.1% phosphorus.

Example 5 A marine diesel engine oil composition was formed by using theproducts of Example 1, 3 and 4. The oil composition was formulated from:

The oils and the several Products were initimately mixed in a blendingtank at about 90 C. for about 2 hours. A clear oil compositionProduct5having the following properties was so formed:

Gravity, API 21.5 S.U.S. 38 C. 1242 S.U.S. 99 C 95 Viscosity index 88Total base number (TBN) 40 Example 6 Another diesel engine oilcomposition was formed with the products of Examples 1, 3, and 4. Theformulation is given below:

Parts Parafiinic-distillate neutral oil, 46.5 S.U.S. a1t99 C.Mid-Continent neutral oil, S.U.S. 99 C 13 Product 1 (CaAc samoosine) 14Product 3 2 Product 4 1 All components were charged to a blending tank,were heated to about 82 C., and were agitated thoroughly until ahomogeneous composition was obtained. Properties of thecompositionProduct 6soprepared, are:

Gravity, API 22.0

S.U.S. 38 C. 1200 S.U.S. 99 C.

Total base number (TBN) 40 TEST DATA Product 5 was subjected to severaltests in order to determine its effectiveness as a cylinder lubricantfor large marine diesel engines. It was so tested on a strictlycomparable basis with a widely used, commercial, high-grade marinediesel oil containing a carbonated basic, calcium sulfurized alkylphenate. The latter oil is identified herein as Commercial Oil A.Results of the several tests are provided below.

Accelerated diesel engine test.-This is a severe CFR diesel engine test.The engine is run under such conditions as: high sulfur fuel; sootycombustion; and a very high blowby level in order to accelerate oilcontamination by the soot and by acidic blowby gases. The tests weremade on S.A.E. 40 grade oils. The engine used is a single cylinder, fourstroke cycle CFR engine modified with a Comet Diesel head; bore 3%inches; displacement, 37.3 cubic inches; compression ratio, 17:1;horsepower output, 6; and crankcase oil, 2500 milliliters plus 1000milliliters for the filter.

Operating conditions of the test include:

Rpm 1'800.

Supercharging 50 Hg absolute, intake air pressure.

Intake air temp. C. 93.

Fuel rate, lb./hr. 5.8.

Smoke level 6.

Blowby 1 55-60 c.f. hr.

High blowby obtained by using four scraper compression rings and aventilated oil ring.

7 Coolant temp. C 100. Oil temp. C 107. Filtration system By-pass.Filter type Cotton waste. Make-up oil, ml./l hrs. 75. Test duration 80hrs.

Test fuel: Special diesel fuel (7% CCR, 2% S) Break-in procedure: 3 hr.break-in with base oil and No.

2 fuel Filter disconnected during break-in.

filter connected before test.

Oil changed and At the beginning and at the end of each test, inspectionis made of the cylinder to determine whether there has been any wear ofthe cylinder bore surface.

Results of the tests made with several oils are given in Table I below.

It is evident from the results shown in Table I that a significantimprovement is obtained with Product 5.

Radioactive piston ring wear test.This permits measurement of pistonring wear rates in a relatively short period of time as no disassemblyof the engine for inspection and wear measurement is required. Briefly,the procedure is as follows. The rings used are made from a single meltof metal. They are activated to a level of approximately 2.5 millicuriesper ring. Iron 59 is the salient radioactive isotope produced.

The engine used is a Bolnes type L diesel engine. It is a two-cylinder,two stroke, single acting diesel engine fitted with a cross-head pistonwhich acts as a scavenge pump and with a Brown-Boveri exhaust gasturbocharger. The engine is equipped to burn light diesel fuel and heavyresidual fuels. In the tests reported here, a residual fuel, sulfurcontent of 3.75%, was used. The cylinder bore is 7.480 inches and thestroke is 13.75 inches. Using special tools and equipment to protectagainst radiation hazards, a radioactive piston ring is installed as thetop compression ring in the No. 2 cylinder of the engine where thehighest pressures, temperatures and wear are encountered.

During the operation of the engine, the radioactive iron worn from thepiston ring is carried by the oil to radiation detection equipment whichis activated by gamma radiation (from iron 59) from ring debris in thecirculating oil. The pulses generated are received by a ratemeter andare translated to counts per minute (c.p.m.) which, in turn, arerecorded as an integrated graph of c.p.m. versus time. Wear rates can beconverted to absolute wear in milligrams per unit of time. To do this, aweighed segment of a piston ring irradiated at the same time as the testring is first converted to an oil-soluble salt, such as ironnaphthenate. An oil blend of this salt is then circulated to thedetector to determine the c.p.m. per milligram of iron present. Astandard curve for decay of iron 59 is drawn, based on a 46.3 day halflife. By comparing the c.p.m./milligram for the test oil and thec.p.m./m. of iron 59 in the iron naphthenate blend, a value of wearexpressed in milligrams of iron per minute can be assigned to the testoil. For purposes of comparison, absolute wear rate values are generallyconverted to milligrams (of iron) per hour. Results are set forth inTable 11 below.

' head, marine diesel.

8 ,TABLE II Wear rate, mgs/hr. Commercial Oil A 6.6

Product 5 3.4

As indicated, the wear rate obtained with Product 5 is only aboutone-half of the rate obtained with Commercial Oil A.

Sea trial.-Product 5 was also tested for an extended period of time inthe cylinders of diesel engines of a commercial motor ship routedbetween Europe and North America. This is a ship of 16,300 tonscapacity, equipped with a main diesel engine. The engine is a Fiat,7-cy1inder, 7578, 2 stroke, single-acting, supercharged, cross-Significant operating conditions observed by regular record keepingwere:

Engine output, H.P. 5900-6900 Speed, r.p.m. 122-128 Cylinder porttemperature, "C 285-310 Exhaust collector temperature, C. 310 Cylinderfeed rate:

kg./cyl./hr., approx. 1 g./ll.P./hr., approx. 1

Product 5 was used to lubricate cylinders 3, 4 and 5 of one of theengines, and Commercial Oil A was used in cylinders 6 and 7 of the sameengine. The amount and type of exhaust port deposits formed were ratedvisually at the end of several voyages, totaling over 1450 mercial Oil Ain the same motor ship is summarized in Table IV, following, whereinaverage exhaust port clogging is reported.

TABLE IV Average Exhaust Port Clogging, percent Hours of LubricationProduct 5 Commercial Oil A 11 Ports cleaned mechanically after 1400hours.

Data given in Tables III and IV reveal a substantial superiority ofProduct 5 over Commercial Oil A. Port clogging is reduced substantially.This constitutes a major commercial advantage since down-time for enginemaintenance purposes represents a loss of about $10,000 per day for ashipowner; less port clogging, of course, requires less down-time forclean-out.

In several other comparative tests wherein determinations were made ofantiscuifing and load carrying properties, and oxidation resistance at163 C. for 40 hours, Product 5 was found to be significantly superior toCommercial Oil A, and to other commercially available products.

t is to be underestood that additional additives can also be present inthe oil compositions, oil concentrates and additive combinationsdescribed and claimed herein.

For example, pour point depressants, viscosity index improvers, rustpreventatives, other detergents, such as ashless detergents, defoamants,etc., can be used in customary concentration. As a particularillustration, a small amount (about 0.0004 percent by weight) of adefoamant, Dow Corning Fluid 200, a silicone composition, can be used inProduct to inhibit foam formation.

Although the invention has been described herein by means of certainspecific embodiments and illustrative examples, it is not intended thatit be limited in any way thereby, but only as indicated in the followingclaims.

We claim: 1. A lubricating oil composition consisting essentially of:

(a) a major proportion of a mineral lubricating oil, (b) from about 1 toabout 20 percent by Weight of the composition of calcium acetate, (c)from about 0.01 to about 3 percent by Weight of the composition of anN-acyl-substituted sarcosine compound of the formula wherein Rrepresents an aliphatic hydrocarbon radical of from 8 to 24 carbonatoms,

(d) from about 0.1 to about percent by weight of the composition of anoil-soluble metal sulfonate, and

(e) from about 0.1 to about 5 percent by weight of the composition of anoil-soluble, phosphorusand sulfur-containing reaction product obtainedby reaction at a temperature between about 100 C. and about 160 C. ofsubstantially one mole of a phosphorus sulfide and four moles of amaterial selected from the group consisting of a dicyclic terpene and anessential oil predominantly comprised of a dicyclic terpene.

2. A composition as defined by claim 1 wherein calcium acetate (b) ispresent in an amount of from about to to about 8 percent by weight.

3. A composition as defined by claim 1 'wherein the sarcosine compound(c) is oleoyl sarcosine.

4. A composition as defined by claim 1 wherein the sarcosine compound(c) is present in an amount of from about 0.1 to about 1 percent byweight.

5. A composition as defined by claim 1 wherein the metal of sulfonate'(d) is calcium.

6. A composition as defined by claim 1 wherein the metal sulfonate (d)is a basic calcium petroleum sulfonate.

7. A composition as defined by claim 1 wherein the metal sulfonate (d)is present in an amount of from about 1 to about 5 percent by weight.

8. A composition as defined by claim 1 wherein the phosphorus sulfideused in forming product (e) is phosphorus pentasulfide.

9. A composition as defined by claim 1 wherein the reaction product (e)is obtained by reaction of substantial- 1y one mole of phosphoruspentasulfide and four moles of pinene at about 150 C.

10. A composition as defined by claim 1 wherein the reaction product (e)is present in an amount of from about 2 to about 3 percent by weight.

11. A lubricating oil composition consisting essentially of:

(a) a major proportion of a mineral lubricating oil,

(b) about 5.6 percent by weight of the composition of calcium acetate,

(c) about 0.42 percent by weight of the composition of oleyl sarcosine,

(d) about 0.8 percent by weight of the composition of an oil-solublecalcium sulfonate,

(e) about 1 percent by weight of the composition of an oil-soluble,phosphorusand sulfur-containing reaction product obtained by reaction ofsubstantially one mole of a phosphorus sulfide and four moles of pineneat about C.

12. A mineral oil concentrate consisting essentially of:

(a) a mineral lubricating oil,

(b) calcium acetate,

(c) an N-acyl-substituted sarcosine compound of the formula wherein Rrepresents an aliphatic hydrocarbon radical of from 8 to 24 carbonatoms,

(d) an oil-soluble metal sulfonate,

(e) an oil soluble, phosphorusand sulfur-containing reaction productobtained by reaction at a temperature between about 100 C. and about C.of substantially one mole of a phosphorus sulfide and four moles of amaterial selected from the group consisting of a dicyclic terpene and anessential oil predominantly comprised of a dicyclic terpene;

the relative quantities of (a) through (e) being such that when saidconcentrate is diluted with mineral lubricating oil the lubricating oilcomposition so formed will contain Approximate Component: weight percent(b) 1-20 13. A composition of matter consisting essentially of:

(a) from about 1 to about 10 parts by weight of calcium acetate,

(b) from about 0.1 to about 1 part by weight of an N-acyl-substitutedsarcosine compound of the formula wherein R represents an aliphatichydrocarbon radical of from 8 to 24 carbon atoms,

(0) from about 0.1 to about 5 parts by weight of an oil-soluble metalsulfonate,

(d) from about 0.1 to about 5 parts by weight of an oil-soluble,phosphorusand sulfur-containing reaction product obtained by reaction ata temperature between about 100 C. and about 160 C. of substantially onemole of a phosphorus sulfide and four moles of a material selected fromthe group consisting of a dicyclic terpene and an essential oilpredominantly comprised of a dicyclic terpene.

14. The composition of claim 1 wherein the metal of sulfonate (d) isselected from the group consisting of calcium, barium and magnesium.

15. The composition of claim 14 wherein the sulfonate is derived from asulfonic acid having a molecular weight of from about 300 to about 800.

References Cited by the Examiner UNITED STATES PATENTS 2,416,281 2/1947Berger et al. 25233.4 2,928,789 3/1960 Sands 252-33.4 2,976,243 3/1961Morway 252-40.7 2,989,464 6/1961 Panzer 25232.5 3,034,907 5/1962Kleernann et a1. 10614 3,182,020 5/1965 Davis 252-40.7 3,206,399 9/1965Davis et al. 252-40.7 X

DANIEL E. WYMAN, Primary Examiner.

E. W. GOLDSTEIN, P. P. GARVIN,

Assistant Examiners.

1. A LUBRICATING OIL COMPOSITION CONSISTING ESSENTIALLY OF: (A) A MAJORPROPORTION OF A MINERAL LUBRICATING OIL, (B) FROM ABOUT 1 TO ABOUT 20PERCENT BY WEIGHT OF THE COMPOSITION OF CALCIUM ACETATE, (C) FROM ABOUT0.01 TO ABOUT 3 PERCENT BY WEIGHT OF THE COMPOSITION OF ANN-ACYL-SUBSTITUTED SARCOSINE COMPOUND OF THE FORMULA